Anionic surfactants and washing agents containing said surfactants

ABSTRACT

Surfactants of general formula (I), in which R 1  denotes a linear or branched alkyl residue having 6 to 20, and in particular 8 to 14 carbon atoms, R 2  denotes H or CH 3 , and M denotes hydrogen, an alkali metal or an N + R 3 R 4 R 5  grouping, in which R 3 , R 4  and R 5 , independently of one another, denote hydrogen, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 2 to 6 carbon atom, can be easily incorporated into washing or cleaning agents, have outstanding application-related properties, and can be produced based on renewable resources.

FIELD OF THE INVENTION

The invention relates to anionic surfactants that can be produced basedon renewable resources and that comprise low critical micelleconcentrations (CMC) and generate low interfacial tensions. Theinvention also relates to a method for producing such surfactants andwashing or cleaning agents comprising these surfactants.

BACKGROUND OF THE INVENTION

The use of surfactants for lowering the surface tension of water, forforming dispersions, and for solubilization has been known, in general,for quite some time in the field of washing and cleaning agents. While alarge number of surfactants are produced entirely or partially based onrenewable resources, some powerful, widely used representatives arestill petrochemically based. Additionally, there is a constant desire toprovide surfactants that have outstanding application-related propertiesso as to be able to achieve high performance, even when using littlesurfactant.

BRIEF SUMMARY OF THE INVENTION

It is the object of the present invention to provide surfactants thatexhibit advantageous application-related properties, such as a low CMCand low surface tension, and that can be produced based on renewableresources. Moreover, the surfactants should exhibit good skincompatibility, and it should also be possible to formulate thesetogether with other surfactants, so as to be suitable, in particular,for use in washing and cleaning agents.

In a first embodiment, the present invention relates to surfactants offormula (I),

in which R¹ denotes a linear or branched alkyl functional group having 6to 20, and in particular 8 to 14 carbon atoms, R² denotes H or CH₃, andM denotes hydrogen, an alkali metal or an N⁺R³R⁴R⁵ grouping, in whichR³, R⁴ and R⁵, independently of one another, denote hydrogen, an alkylgroup having 1 to 6 carbon atoms or a hydroxyalkyl group having 2 to 6carbon atoms. Surfactants of general formula (I) can be produced by wayof O-alkylation of the hydroxypropyl group of4-(3-hydroxypropyl)-guaiacol or 4-(3-hydroxypropyl)-2-methoxyanisole andsubsequent sulfonation, and optionally neutralization by way ofsubsequent reaction with MOH, where M denotes an alkali metal or anN⁺R³R⁴R⁵ grouping, in which R³, R⁴ and R⁵, independently of one another,denote hydrogen, an alkyl group having 1 to 6 carbon atoms or ahydroxyalkyl group having 2 to 6 carbon atoms. The invention furthermorerelates to this method for producing a compound of general formula (I),4-(3-hydroxypropyl)-guaiacol, as described in Angew. Chem. Int. Ed.2014, 53, pages 8634 to 8639, can be obtained from wood by way ofcatalytic biorefinery. 4-(3-hydroxypropyl)-guaiacol can be isolated asthe main component from the phenolic components created during thecatalytic reaction of wood. In the case of spruce wood, the yield of4-(3-hydroxypropyl)-guaiacol ranges between 5 wt. % and 9 wt. %, basedon the wood used.

The surfactants according to the invention have very low CMC values andresult in very low interfacial tensions with respect to oil, exhibitingfast dynamics in terms of the organization at the interface.Particularly preferred surfactants according to the invention, in waterat a pH of 8.5 and 25° C., have a CMC of 0.01 g/l to 1.0 g/l and, at aconcentration of 1 g/l in water at a pH of 8.5 and 25° C., generateinterfacial tension of no more than 2.5 mN/m, determinable by way of thespinning drop method (20-minute equilibration time) against triolein.

The surfactants according to the invention can be obtained fromrenewable resources as described. Additionally, they have the advantagethat the renewable resources from which they can be derived do not formthe basis for producing food, so that a situation in which these competewith foodstuffs, as found with some other renewable resources, does notexist here.

The surfactants according to the invention of general formula (I), whereR²═H, are preferably produced, proceeding from4-(3-hydroxypropyl)-guaiacol, by way of O-alkylation of thehydroxypropyl group after inserting a protecting group, such as a benzylgroup, for the OH group present at the aromatic compound, and subsequentcleaving of the protecting group so as to release the OH group presentat the aromatic compound, followed by sulfonation. It is not necessaryto insert and remove a corresponding protecting group when producingsurfactants according to the invention where R²═CH₃. In the first case,preferably an excess, for example of 1.2 mole to 1.8 mole based on 1mole 4-(3-hydroxypropyl)-guaiacol, of benzyl halide, and in particularbenzyl bromide, and an excess, for example of 2.5 mole to 2.5 mole basedon 1 mole 4-(3-hydroxypropyl)-guaiacol, of a base, such as potassiumcarbonate, are added to 4-(3-hydroxypropyl)-guaiacol in a suitablesolvent, such as acetone, and heated until the reaction has beencompleted, for example heated in acetone under reflux. The resultantbenzyl ether derivative can be isolated, if necessary by way ofdistillation, such as by way of Kugelrohr (“ball tube”) distillation,from the optionally filtered reaction mixture, from which the solventmay have been removed, for example by distilling off, at reducedpressure. The derivative is preferably mixed in a suitable solvent, suchas dimethyl sulfoxide, with a base, such as potassium-tert-butanolate,and an alkyl halide R¹-Hal, wherein Hal denotes chlorine, bromine,iodine or the mixtures thereof, and heated, for example to 60° C. Aftercooling, the product can be obtained, for example by way of extractionusing a suitable solvent, such as methyl-tert-butyl ether, andpurification by way of column chromatography, if necessary. Using asuitable solvent, such as tetrahydrofuran, and a hydrogenation catalyst,such as palladium on carbon (Pd/C, 5%), the benzyl protecting group iscleaved off this product by the application of hydrogen pressure (suchas 5 bar), for example at 40° C. for 8 hours. If desired, the productmay be purified by way of column chromatography. It is mixed at areduced temperature, such as 5° C., with a sulfonating agent, such as98% H₂SO₄, then heated to room temperature, if necessary, and, when thereaction has been completed, which may be tracked by way of thin filmchromatography, for example, is neutralized using an aqueous MOHsolution, if necessary after being placed in ice water, wherein M hasthe meaning indicated above. Thereafter, water can be removed by way ofdistillation, the residue can be received in a suitable solvent, such asmethanol, the resulting solution can be filtered, and the surfactant ofgeneral formula (I), where R²═H, can be obtained after removal of thesolvent.

To produce surfactants according to the invention of general formula(I), where R²═CH₃, preferably an excess of likewise4-(3-hydroxypropyl)-guaiacol is used, which is mixed with an excess, forexample of 1.5 mole to 2.5 mole based on 1 mole4-(3-hydroxypropyl)-guaiacol, of methyl halide, and in particular methyliodide, and an excess, for example of 2.5 mole to 3.5 mole based on 1mole 4-(3-hydroxypropyl)-guaiacol, of a base, such as potassiumcarbonate, in a suitable solvent, such as acetone, and heated until thereaction has been completed, for example heated in acetone under reflux.After cooling, the product can be obtained, for example, by way ofextraction using a suitable solvent, such as methyl-tert-butyl ether,and optionally distillation, and in particular at reduced pressure. Thisproduct can, in principle, be alkylated as described above for theproduction of surfactants according to the invention of general formula(I), where R²═H, by reacting it with alkyl halide, and it can besulfonated by reacting it sulfuric acid, and optionally it can beneutralized with aqueous MOH solution.

The surfactants according to the invention are excellently suited asingredients in washing and cleaning agents, cosmetics such as shampoos,toothpastes, and for the remaining fields of application in whichpreviously anionic surfactants have customarily been used, such as inthe food industry, geoscience, tertiary crude oil recovery, polymertechnology, metal working, photography, paper recycling, tool cleaningand firefighting.

Particularly good results are achieved when these are used in washingand cleaning agents, so that the present invention furthermore relatesto the use of anionic surfactant of general formula (I) for producingwashing or cleaning agents, to the use of an anionic surfactant ofgeneral formula (I) for increasing the performance of washing orcleaning agents when washing laundry or cleaning hard surfaces, and towashing or cleaning agents that comprise a surfactant of general formula(I).

An agent according to the invention preferably comprises 1 wt. % to 99wt. %, in particular 3 wt. % to 85 wt. %, and particularly preferably 5wt. % to 65 wt. % of the surfactant of general formula (I).

In addition to the anionic surfactant of general formula (I), thewashing or cleaning agent can comprise further ingredients that furtherimprove the application-related and/or aesthetic properties of theagent. Within the scope of the present invention, the agent preferablyadditionally comprises one or more substances from the group consistingof non-ionic surfactants, anionic surfactants, builders, bleachingagents, bleach activators, enzymes, electrolytes, pH-setting agents,perfumes, perfume carriers, fluorescing agents, dyes, hydrotropicsubstances, suds suppressors, anti-redeposition agents, grayinginhibitors, shrinkage preventers, anti-wrinkle agents, dye transferinhibitors, antimicrobial active ingredients, non-aqueous solvents,germicides, fungicides, antioxidants, preservatives, corrosioninhibitors, antistatic agents, bittering agents, ironing aids,repellents and impregnating agents, active skin care ingredients,swelling and anti-slip agents, softening components and UV absorbers.

In addition to the anionic surfactant of general formula (I), the agentaccording to the invention preferably comprises up to 99 wt. %, inparticular 2 wt. % to 85 wt. %, and particularly preferably 5 wt. % to65 wt. % further surfactants, wherein the additionally presentsurfactants preferably can likewise be obtained from renewableresources.

The agent according to the invention can comprise non-ionic surfactants.Suitable non-ionic surfactants include alkoxylated fatty alcohols,alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylatedfatty acid amides, polyhydroxy fatty acid amides, alkylphenol polyglycolethers, amine oxides, alkylpolyglucosides and mixtures thereof.

Preferred alkoxylated fatty alcohols are ethoxylated, in particularprimary alcohols preferably having 8 to 18 carbon atoms, and on average4 to 12 moles ethylene oxide (EO) per mole of alcohol, in which thealcohol residue is linear. In particular, alcohol ethoxylates having 12to 18 carbon atoms, for example from coconut, palm, tallow fatty oroleyl alcohol, and an average of 5 to 8 EO per mole of alcohol areparticularly preferred. The preferred ethoxylated alcohols include, forexample C₁₂₋₁₄ alcohols having 4 EO or 7 EO, C₉₋₁₁ alcohols having 7 EO,C₁₂₋₁₈ alcohols having 5 EO or 7 EO, and mixtures thereof. The indicateddegrees of ethoxylation represent statistical averages that cancorrespond to an integer or a fractional number for a specific product.Preferred alcohol ethoxylates exhibit a restricted distribution ofhomologs (narrow range ethoxylates, NRE). In addition to these non-ionicsurfactants, fatty alcohols having more than 12 EO can also be used.Examples of these are tallow fatty alcohol having 14 EO, 25 EO, 30 EO,or 40 EO. According to the invention, it is also possible to usenon-ionic surfactants that contain EO and PO groups together in themolecule. Also suitable is a mixture of a (more strongly) branchedethoxylated fatty alcohol and an unbranched ethoxylated fatty alcohol,such as a mixture of a C₁₆₋₁₈ fatty alcohol having 7 EO and2-propylheptanol having 7 EO. The amount of non-ionic surfactant ispreferably up to 25 wt. %, and in particular 1 wt. % to 20 wt. %,wherein the information in percent by weight, here and hereafter, isbased on the total washing agent, unless indicated otherwise.

Possibly additionally present anionic surfactants comprise alkyl benzenesulfonic acid salts, olefin sulfonic acid salts, C₁₂₋₁₈ alkane sulfonicacid salts, salts of sulfuric acid monoesters with a fatty alcohol, afatty acid soap, salts of sulfuric acid monoesters with an ethoxylatedfatty alcohol, or a mixture of two or more of these anionic surfactants.

Surfactants of the sulfonate type that can be used are, for example,C₉₋₁₃ alkylbenzene sulfonates, olefin sulfonates, which is to saymixtures of alkene and hydroxyalkane sulfonates, and disulfonates, asthey are obtained, for example, from C₁₂₋₁₈ monoolefins having aterminal or internal double bond by way of sulfonation with gaseoussulfur trioxide and subsequent alkaline or acid hydrolysis of thesulfonation products. Also suitable are C₁₂₋₁₈ alkane sulfonates and theesters of α-sulfofatty acids (ester sulfonates), for example theα-sulfonated methyl esters of hydrogenated coconut, palm kernel ortallow fatty acids.

The salts of the sulfuric acid half-esters of C₁₂-C₁₈ fatty alcohols,for example from coconut fatty alcohol, tallow fatty alcohol, lauryl,myristyl, cetyl or stearyl alcohol, or of C₁₀-C₂₀ oxo alcohols and thehalf-esters of secondary alcohols having this chain length are preferredalk(en)yl sulfates. From a washing perspective, the C₁₂-C₁₆ alkylsulfates, C₁₂-C₁₅ alkyl sulfates, and C₁₄-C₁₅ alkyl sulfates arepreferred.

Fatty alcohol ether sulfates, such as the sulfuric acid monoesters ofstraight-chain or branched C₇₋₂₁ alcohols ethoxylated with 1 to 6 molesof ethylene oxide, such as 2-methyl-branched C₉₋₁₁ alcohols having, onaverage, 3.5 moles ethylene oxide (EO) or C₁₂₋₁₈ fatty alcohols having 1to 4 EO, are also suited.

Further suitable anionic surfactants are fatty acid soaps. Saturated andunsaturated fatty acid soaps are suitable, such as the salts of lauricacid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucicacid and behenic acid, and in particular soap mixtures derived fromnatural fatty acids, such as coconut, palm kernel, olive oil, or tallowfatty acids.

The additional anionic surfactants, including the fatty acid soaps, maybe present in the form of the sodium, potassium, magnesium or ammoniumsalts thereof. The anionic surfactants are preferably present in theform of the sodium salts or ammonium salts thereof. Amines that may beused for neutralization preferably include choline, triethylamine,monoethanolamine, diethanolamine, triethanolamine, methylethylamine, ora mixture thereof, wherein monoethanolamine is preferred. In aparticularly preferred embodiment, the agent comprises alkyl benzenesulfonic acid neutralized with monoethanolamine, and in particular C₉₋₁₃alkyl benzene sulfonic acid, and/or fatty acid neutralized withmonoethanolamine, in particular when the agent is present in liquidform.

The content of additional anionic surfactant, if the same is present, inthe agent according to the invention is preferably up to 30 wt. %, andin particular 1 wt. % to 25 wt. %.

DETAILED DESCRIPTION OF THE INVENTION

An agent according to the invention preferably comprises at least onewater-soluble and/or water-insoluble, organic and/or inorganic builder.The water-soluble organic builder substances include polycarboxylicacids, in particular citric acid and saccharic acids, monomeric andpolymeric aminopolycarboxylic acids, in particular glycine diaceticacid, methylglycine diacetic acid, nitrilotriacetic acid,iminodisuccinates such as ethylenediamine-N,N′-disuccinic acid andhydroxyiminodisuccinates, ethylenediaminetetraacetic acid andpolyaspartic acid, polyphosphonic acids, in particularaminotris(methylenephosphonic acid),ethylenediaminetetrakis(methylenephosphonic acid), lysinetetra(methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonicacid, polymeric hydroxy compounds such as dextrin and polymeric(poly-)carboxylic acids, in particular polycarboxylates accessible byoxidation of polysaccharides, polymeric acrylic acids, methacrylicacids, maleic acids, and mixed polymers of the same, which may also havesmall fractions of polymerizable substances having no carboxylic acidfunctionality polymerized into the same. The relative average molar massof the homopolymers of unsaturated carboxylic acids is generally between5,000 g/mol and 200,000 g/mol, that of the copolymers is between 2,000g/mol and 200,000 g/mol, and preferably 50,000 g/mol to 120,000 g/mol,each based on free acid. A particularly preferred acrylic acid/maleicacid copolymer has a relative average molar mass of 50,000 to 100,000.Suitable, albeit less preferred compounds of this class are copolymersof acrylic acid or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in whichthe proportion of the acid is at least 50 wt. %. It is also possible touse terpolymers comprising two unsaturated acids and/or the saltsthereof as the monomers, and vinyl alcohol and/or a vinyl alcoholderivative or a carbohydrate as the third monomer, as water-solubleorganic builder substances. The first acidic monomer or the salt thereofis derived from a monoethylenically unsaturated C₃-C₈ carboxylic acidand preferably from a C₃-C₄ monocarboxylic acid, in particular from(meth)acrylic acid. The second acidic monomer or the salt thereof can bea derivative of a C₄-C₈ dicarboxylic acid, wherein maleic acid isparticularly preferred. The third monomeric unit is formed in this caseby vinyl alcohol and/or preferably an esterified vinyl alcohol. Inparticular, vinyl alcohol derivatives are preferred which represent anester of short-chain carboxylic acids, for example of C₁-C₄ carboxylicacids, with vinyl alcohol. Preferred polymers comprise 60 wt. % to 95wt. %, in particular 70 wt. % to 90 wt. %, (meth)acrylic acid or(meth)acrylate, and particularly preferably acrylic acid or acrylate,and maleic acid or maleinate, and 5 wt. % to 40 wt. %, preferably 10 wt.% to 30 wt. %, vinyl alcohol and/or vinyl acetate. Most particularlypreferred are polymers in which the weight ratio of (meth)acrylic acidor (meth)acrylate to maleic acid or maleinate ranges between 1:1 and4:1, preferably between 2:1 and 3:1, and in particular 2:1 and 2.5:1.Both the amounts and the weight ratios are based on the acids. Thesecond acidic monomer or the salt thereof can also be a derivative of anallyl sulfonic acid, which at the 2-position is substituted with analkyl functional group, preferably a C₁-C₄ alkyl functional group, or anaromatic functional group, which is preferably derived from benzene orbenzene derivatives. Preferred terpolymers contain 40 wt. % to 60 wt. %,in particular 45 wt. % to 55 wt. %, (meth)acrylic acid or(meth)acrylate, particularly preferably acrylic acid or acrylate, 10 wt.% to 30 wt. %, preferably 15 wt. % to 25 wt. %, methallyl sulfonic acidor methallyl sulfonate, and, as the third monomer, 15 wt. % to 40 wt. %,preferably 20 wt. % to 40 wt. % of a carbohydrate. This carbohydrate canbe a monosaccharide, disaccharide, oligosaccharide or polysaccharide,for example, wherein monosaccharides, disaccharides or oligosaccharidesare preferred. Sucrose is particularly preferred. As a result of the useof the third monomer, predetermined breaking points are presumablyintroduced into the polymer, which are responsible for the goodbiodegradability of the polymer. These terpolymers generally have arelative average molar mass between 1,000 g/mol and 200,000 g/mol, andpreferably between 200 g/mol and 50,000 g/mol. Further preferredcopolymers are those that contain acrolein and acrylic acid/acrylic acidsalts or vinyl acetate as monomers. The organic builders can be used inthe form of aqueous solutions, and preferably in the form of 30 to 50percent by weight aqueous solutions, in particular for the production ofliquid agents. All aforementioned acids are generally used in the formof the water-soluble salts thereof, and in particular of the alkalisalts thereof.

Such organic builders can be present in amounts up to 40 wt. %, inparticular up to 25 wt. %, and preferably from 1 wt. % to 8 wt. %, ifdesired. Amounts in the upper half of the aforementioned ranges arepreferably used for pasty or liquid, in particular hydrous, agents.

Water-soluble inorganic builder materials that can be used are inparticular polyphosphates, and preferably sodium triphosphate.Water-insoluble inorganic builder materials that are used are inparticular crystalline or amorphous, water-dispersible alkalialuminosilicates, in amounts not above 25 wt. %, preferably from 3 wt. %to 20 wt. %, and in particular in amounts from 5 wt. % to 15 wt. %.Among these, the crystalline sodium aluminosilicates in washing agentquality, in particular zeolite A, zeolite P and zeolite MAP, andoptionally zeolite X, are preferred. Amounts close to the aforementionedupper limit are preferably used in solid, particulate agents. Suitablealuminosilicates, in particular, do not comprise any particles having aparticle size above 30 μm, and preferably have a content of at least 80wt. % of particles having a size of less than 10 μm. The calcium-bindingcapacity is generally in the range of 100 to 200 mg CaO per gram.

In addition, or as an alternative to the described water-insolublealuminosilicate and alkali carbonate, further water-soluble inorganicbuilder materials may be present. In addition to the polyphosphates suchas sodium triphosphate, these include in particular the water-solublecrystalline and/or amorphous alkali silicate builders. The agentspreferably comprise such water-soluble inorganic builder materials inamounts of 1 wt. % to 20 wt. %, and in particular 5 wt. % to 15 wt. %.The alkali silicates that can be used as builder materials preferablyhave a molar ratio of alkali oxide to SiO₂ of less than 0.95, inparticular of 1:1.1 to 1:12 and can be present in amorphous orcrystalline form. Preferred alkali silicates are sodium silicates, andin particular the amorphous sodium silicates, having a molar ratio ofNa₂O:SiO₂ of 1:2 to 1:2.8. Crystalline silicates, which may be presenteither alone or in a mixture with amorphous silicates, that are used arepreferably crystalline phyllosilicates of general formulaNa₂Si_(x)O_(2x+1)·y H₂O, where x, the so-called module, is a number from1.9 to 4, and y is a number from 0 to 20, and preferred values for x are2, 3 or 4. Preferred crystalline phyllosilicates are those in which x inthe above-mentioned general formula takes on the value 2 or 3. Inparticular, both β- and δ-sodium disilicates (Na₂Si₂O₅.y H₂O) arepreferred. Practically anhydrous crystalline alkali silicates, producedfrom amorphous alkali silicates, of the above general formula, in whichx denotes a number from 9 to 2.1, can also be used in the agents. In afurther preferred embodiment, a crystalline sodium phyllosilicate havinga module of 2 to 3 is used, as it can be produced from sand and soda.Sodium silicates having a module in the range from 1.9 to 3.5 are usedin a further embodiment. In a preferred embodiment of such agents, agranular compound composed of alkali silicate and alkali carbonate isused, as is commercially available under the name Nabion® 15, forexample.

Possible suitable peroxide bleaching agents include in particularorganic peroxy acids or peracid salts of organic acids, such asphthalimidopercaproic acid, perbenzoic acid, monoperoxyphthalic acid anddiperdodecanoic diacid and the salts thereof, such as magnesiummonoperoxyphthalate, diacyl peroxides, hydrogen peroxide and inorganicsalts giving off hydrogen peroxide under the usage conditions, such asalkali perborate, alkali percarbonate and/or alkali persilicate, andhydrogen peroxide clathrates, such as H₂O₂ urea adducts. Hydrogenperoxide may also be created by way of an enzymatic system, which is tosay an oxidase and the substrate thereof. To the extent that solidperoxygen compounds are to be used, these may be used in the form ofpowders or granules, which may also be coated in the manner known perse. The use of alkali percarbonate, alkali perborate monohydrate orhydrogen peroxide is particularly preferred. A washing agent that can beused within the scope of the invention comprises a peroxide bleachingagent in amounts of preferably up to 60 wt. %, in particular of 5 wt. %to 50 wt. %, and particularly preferably of 15 wt. % to 30 wt. %, oralternatively of 2.5 wt. % to 20 wt. %, wherein the particularlypreferred peroxide bleaching agent in liquid agents is hydrogenperoxide, and in solid agents it is sodium percarbonate. Peroxidebleaching agent particles preferably have a particle size in the rangeof 10 μm to 5000 μm, and in particular of 50 μm to 1000 μm, and/or adensity of 0.85 g/cm³ to 4.9 g/cm³, and in particular of 0.91 g/cm³ to2.7 g/cm³.

In particular, compounds that, under perhydrolysis conditions, yieldoptionally substituted perbenzoic acid and/or aliphatic peroxocarboxylicacids having 1 to 12 carbon atoms, and in particular 2 to 4 carbonatoms, either alone or in mixtures, can be used as the bleach-activatingcompound yielding peroxocarboxylic acid under perhydrolysis conditions.Suitable bleach activators are those that carry 0- and/or N-acyl groups,in particular having the described carbon atomic number and/oroptionally substituted benzoyl groups. Polyacylated alkylenediamines, inparticular tetra acetyl ethylene diamine (TAED), acylated glycolurils,in particular tetraacetyl glycoluril (TAGU), acylated triazinederivatives, in particular1,5-diacetyl-2,4-dioxohexahydro-1,3.5-triazine (DADHT), N-acylimides, inparticular N-nonanoyl succinimide (NOSI), acylated phenolsulfonates orphenolcarboxylates or the sulfonic or carboxylic acids of these, inparticular nonanoyl or iso-nonanoyl or lauroyl oxybenzene sulfonate(NOBS or iso-NOBS or LOBS), or decanoyloxybenzoate (DOBA), the formalcarboxylic acid ester derivatives thereof, such as4-(2-decanoyloxyethoxycarbonyloxy)benzene sulfonate (DECOBS), acylatedpolyhydric alcohols, in particular triacetin, ethylene glycol diacetateand 2,5-diacetoxy-2,5-dihydrofuran, and acetylated sorbitol and mannitoland the mixtures thereof (SORMAN), acylated sugar derivatives, inparticular penta-acetyl glucose (PAG), penta-acetyl fructose,tetra-acetyl xylose and octa-acetyl lactose, acetylated, optionallyN-alkylated glucamine and gluconolactone, and/or N-acylated lactams, forexample N-benzoyl caprolactam, are preferred.

In addition to or instead of the compounds that, under perhydrolysisconditions, form peroxocarboxylic acids, further bleach-activatingcompounds, such as nitriles, which yield perimidic acids underperhydrolysis conditions, may be present. These include, in particular,aminoacetonitrile derivatives comprising a quaternized nitrogen atomaccording to formula

in which R¹ denotes —H, —CH₃, a C₂₋₂₄ alkyl or alkenyl functional group,a substituted C₁₋₂₄ alkyl functional group or C₂₋₂₄ alkenyl functionalgroup comprising at least one substituent from the group —Cl, —Br, —OH,—NH₂, CN and —N⁽⁺⁾—CH₂—CN, an alkyl or alkenyl aryl functional grouphaving a C₁₋₂₄ alkyl group, or a substituted alkyl or alkenyl arylfunctional group having at least one, preferably two, optionallysubstituted C₁₋₂₄ alkyl groups and optionally further substituents onthe aromatic ring, R² and R³, independently of one another, are selectedfrom —CH₂—CN, —CH₃, —CH₂—CH₃, —CH₂—CH₂—CH₃, —CH(CH₃)—CH₃, —CH₂—OH,—CH₂—CH₂—OH, —CH(OH)—CH₃, —CH₂—CH₂—CH₂—OH, —CH₂—CH(OH)—CH₃,—CH(OH)—CH₂—CH₃, —(CH₂CH₂—O)_(n)H, where n=1, 2, 3, 4, 5 or 6, R⁴ andR⁵, independently of one another, have a meaning stated above for R¹, R²or R³, wherein at least two of the aforementioned functional group, inparticular R² and R³, may be linked to one another so as to close thering, including the nitrogen atom and optionally further heteroatoms,and then preferably form a morpholino ring, and X is a charge-equalizinganion, preferably selected from benzene sulfonate, toluene sulfonate,cumol sulfonate, the C₉₋₁₅ alkylbenzene sulfonates, the C₁₋₂₀ alkylsulfates, the C₈₋₂₂ carboxylic acid methyl ester sulfonates, sulfate,hydrogen sulfate, and the mixture thereof, can be used. Bleachactivators forming peroxocarboxylic acids or perimidic acids underperhydrolysis conditions are preferably present in amounts up to 25 wt.%, and in particular 0.1 wt. % to 10 wt. % in the agents according tothe invention. Bleach activator particles preferably have a particlesize in the range of 10 μm to 5000 and in particular of 50 μm to 1000and/or a density of 0.85 g/cm³ to 4.9 g/cm³, and in particular of 0.91g/cm³ to 2.7 g/cm³.

It is possible for bleach-catalyzing transition metal complexes to bepresent, either in addition to or instead of the aforementioned bleachactivators. These are preferably selected among the cobalt, iron,copper, titanium, vanadium, manganese and ruthenium complexes. Possibleligands in such transition metal complexes are either inorganic ororganic compounds, which in addition to carboxylates, include inparticular compounds having primary, secondary and/or tertiary amineand/or alcohol functions, such as pyridine, pyridazine, pyrimidine,pyrazine, imidazole, pyrazole, triazole, 2,2′-bispyridyl amine,tris-(2-pyridylmethyl)amine, 1,4,7-triazacyclononane,1,4,7-trimethyl-1,4,7-triazacyclononane,1,5,9-trimethyl-1,5,9-triazacyclododecane,(bis-((1-methylimidazol-2-yl)-methyl))-(2-pyridylmethyl)amine,N,N′-(bis-(1-methylimidazol-2-yl)-methyl)ethylenediamine,N-bis-(2-benzimidazolylmethyl)amino ethanol,2,6-bis-(bis-(2-benzimidazolylmethyl)aminomethyl)-4-methylphenol,N,N,N′,N′-tetrakis-(2-benzimidazolylmethyl)-2-hydroxy-1,3-diaminopropane,2,6-bis-(bis-(2-pyridyl-methyl)aminomethyl)-4-methylphenol,1,3-bis-(bis-(2-benzimidazolylmethyl)aminomethyl)benzene, sorbitol,mannitol, erythritol, adonitol, inositol, lactose, and optionallysubstituted salenes, porphins and porphyrins. The inorganic neutralligands include in particular ammonia and water. If not all coordinationsites of the central transition metal atom are occupied by neutralligands, the complex comprises further, preferably anionic and, amongthese, in particular monodentate or bidentate, ligands. These include,in particular, the halides, such as fluoride, chloride, bromide andiodide, and the (NO₂)⁻ group, which is to say a nitro ligand or anitrito ligand. The (NO₂)⁻ group can also be bound to a transition metalin a chelating manner, or it may asymmetrically or μ¹-O bridge twotransition metal atoms. In addition to the above-mentioned ligands, thetransition metal complexes can carry further ligands, which generallyhave simpler structures, and in particular monovalent or polyvalentanionic ligands. For example, nitrate, acetate, trifluoroacetate,formate, carbonate, citrate, oxalate, perchlorate and complex anionssuch as hexafluorophosphate may be used. The anionic ligands are toensure the charge equalization between the central transition metal atomand the ligand system. The presence of oxo ligands, peroxo ligands andimino ligands is also possible. In particular, these ligands may alsohave a bridging effect, whereby multinuclear complexes are created. Inthe case of bridged, binuclear complexes, the two metal atoms in thecomplex do not have to be identical. It is also possible to usebinuclear complexes in which the two central transition metal atoms havediffering oxidation numbers. If anionic ligands are absent or thepresence of anionic ligands does not result in charge equalization inthe complex, anionic counterions are present in the transition metalcomplex compounds to be used according to the invention, whichneutralize the cationic transition metal complex. These anioniccounterions include in particular nitrate, hydroxide,hexafluorophosphate, sulfate, chlorate, perchlorate, the halides such aschloride, or the anions of carboxylic acids such as formate, acetate,oxalate, benzoate or citrate. Examples of transition metal complexcompounds that may be used include[N,N′-bis[(2-hydroxy-5-vinylphenyl)-methylene]-1,2-diamino-cyclohexane]-manganese-(III)-chloride,[N,N′-bis[(2-hydroxy-5-nitrophenyl)-methylene]-1,2-diamino-cyclohexane]-manganese-(111)-acetate,[N,N′-bis[(2-hydroxyphenyl)-methylene]-1,2-phenylendiamine]-manganese-(111)-acetate,[N,N′-bis[(2-hydroxyphenyl)-methylene]-1,2-diaminocyclohexane]-manganese-(111)-chloride,[N,N′-bis[(2-hydroxyphenyl)-methylene]-1,2-diaminoethane]-manganese-(111)-chloride,[N,N′-bis[(2-hydroxy-5-sulfonatophenyl)-methylene]-1,2-diaminoethane]-manganese-(111)-chloride,manganese-oxalato complexes, nitropentamminecobalt(111) chloride,nitritopentamminecobalt(111) chloride, hexamminecobalt(111) chloride,chloropentamminecobalt(111) chloride, and the peroxo complex[(NH₃)₅Co—O—O—Co(NH₃)₅]Cl₄.

Enzymes that can be used in the agents include those of the class ofproteases, amylases, lipases, cutinases, pullulanases, hemicellulases,cellulases, oxidases, laccases and peroxidases, and the mixturesthereof. Particularly suited are enzymatic active ingredients obtainedfrom fungi or bacteria, such as Bacillus subtilis, Bacilluslicheniformis, Bacillus lentus, Streptomyces griseus, Humicolalanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes,Pseudomonas cepacia or Coprinus cinereus. The enzymes can be adsorbed oncarrier substances and/or be embedded in coating substances to protectthem against premature inactivation. These are preferably present in thewashing or cleaning agents according to the invention in amounts up to 5wt. %, and in particular of 0.002 wt. % to 4 wt. %. If the agentaccording to the invention comprises protease, this preferably has aproteolytic activity in the range of approximately 100 PE/g toapproximately 10,000 PE/g, and in particular 300 PE/g to 8000 PE/g. Ifseveral enzymes are to be used in the agent according to the invention,this may be carried out by incorporating two or more enzymes that areseparate or separately formulated in the known manner, or by two or moreenzymes that are formulated together in granules.

To set a desired pH value that does not result on its own by virtue ofmixing the remaining components, the agents according to the inventioncan comprise system-compatible and environmentally friendly acids, inparticular citric acid, acetic acid, tartaric acid, malic acid, lacticacid, glycolic acid, succinic acid, glutaric acid and/or adipic acid,but also mineral acids, in particular sulfuric acid, or bases, inparticular ammonium hydroxides or alkali hydroxides. Such pH regulatorsare preferably present in the agents according to the invention inamounts not above 20 wt. %, and in particular of 1.2 wt. % to 17 wt. %.

The task of graying inhibitors is to maintain the dirt dissolved fromthe textile fibers suspended in the liquor. Water-soluble colloids,usually of an organic nature, are suitable for this purpose, such asstarch, sizing material, gelatin, salts of ether carboxylic acids orether sulfonic acids of starch or cellulose, or salts of acidic sulfuricacid esters of cellulose or starch. Water-soluble, acid group-containingpolyamides are also suitable for this purpose.

Furthermore, starch derivatives other than those mentioned above may beused, for example aldehyde starches. The use of cellulose ethers, suchas carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkylcellulose and mixed ethers, such as methyl hydroxyethyl cellulose,methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and themixtures thereof, for example in amounts of 0.1 to 5 wt. %, based on theagents, is preferred.

If desired, the agents can comprise a customary dye transfer inhibitor,preferably in amounts up to 2 wt. %, and in particular of 0.1 wt. % to 1wt. %, which in a preferred embodiment is selected from the polymers ofvinylpyrrolidone, vinylimidazole, vinylpyridine-N-oxide, or thecopolymers of these. It is possible to use both polyvinylpyrrolidoneshaving molecular weights of 15,000 g/mol to 50,000 g/mol andpolyvinylpyrrolidones having higher molecular weights of more than1,000,000 g/mol, and in particular of 1,500,000 g/mol to 4,000,000g/mol, for example, N-vinylimidazole/N-vinylpyrrolidone copolymers,polyvinyloxazolidones, copolymers based on vinyl monomers and carboxylicacid amides, pyrrolidone group-comprising polyesters and polyamides,grafted polyamidoamines and polyethylene imines, polyamine-N-oxidepolymers and polyvinyl alcohols. However, it is also possible to useenzymatic systems, comprising a peroxidase and hydrogen peroxide or asubstance yielding hydrogen peroxide in water. The addition of amediator compound for the peroxidase, for example of an acetosyringone,a phenol derivative or a phenothiazine or phenoxazine, is preferred inthis case, wherein in addition the above-mentioned polymeric dyetransfer inhibitor active ingredients can also be used.Polyvinylpyrrolidone preferably has an average molar mass in the rangeof 10,000 g/mol to 60,000 g/mol, and in particular in the range of25,000 g/mol to 50,000 g/mol. Among the copolymers, those composed ofvinylpyrrolidone and vinylimidazole in a molar ratio of 5:1 to 1:1,having an average molar mass in the range of 5,000 g/mol to 50,000g/mol, and in particular of 10,000 g/mol to 20,000 g/mol, are preferred.In preferred embodiments of the invention, however, the washing agentsare free from such added dye transfer inhibitors.

Washing agents can comprise derivatives of diaminostilbene disulfonicacid or the alkali metal salts thereof, for example, as opticalbrighteners, although they are preferably free from optical brightenerswhen used as washing agents for colored textiles. For example, salts of4,4′-bis(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)stilbene-2,2′-disulfonicacid or similarly structured compositions are suitable, which carry adiethanolamino group, a methylamino group, an anilino group or a2-methoxyethylamino group instead of the morpholino group. Moreover,brighteners of the type of substituted diphenylstyryls can be present,for example the alkali salts of 4,4′-bis(2-sulfostyryl)biphenyl,4,4′-bis(4-chloro-3-sulfostyryl)biphenyl, or4-(4-chlorostyryl)-4′-(2-sulfostyryl)biphenyls. It is also possible touse mixtures of the aforementioned optical brighteners.

In particular when used with mechanical processes, it may beadvantageous to add customary suds suppressors to the agents. Forexample, soaps of natural or synthetic origin having a high content ofC₁₈-C₂₄ fatty acids are suitable suds suppressors. Suitablenon-surfactant-type suds suppressors are, for example,organopolysiloxanes and the mixtures thereof with micro-fine, optionallysilanized silicic acid and paraffins, waxes, microcrystalline waxes andthe mixtures thereof with silanized silicic acid or bis-fatty acidalkylene diamides. Advantageously, mixtures of different sudssuppressors are also used, for example those composed of silicones,paraffins or waxes. The suds suppressors, and in particularsilicone-comprising and/or paraffin-comprising suds suppressors, arepreferably bound to a granular carrier substance that is soluble ordispersible in water. In particular, mixtures of paraffins and ethylenedistearylamide are preferred.

In a preferred embodiment, the agent according to the invention isparticulate and, in addition to the surfactant of general formula (I),comprises builders, in particular in an amount in the range of 1 wt. %to 60 wt. %.

In a further preferred embodiment, an agent according to the inventionis liquid and comprises 1 wt. % to 90 wt. %, in particular 10 wt. % to85 wt. %, preferably 25 wt. % to 75 wt. %, and particularly preferably35 wt. % to 65 wt. % water, water-miscible solvent or a mixture of waterand water-miscible solvent. Water-miscible solvents include, forexample, monohydric alcohols comprising 1 to 4 carbon atoms, inparticular methanol, ethanol, isopropanol and tert-butanol, diols andtriols comprising 2 to 4 carbon atoms, in particular ethylene glycol,propylene glycol and glycerol, and the mixtures thereof and ethersthereof derivable from the aforementioned compound classes. Suchwater-miscible solvents are preferably present in the agents accordingto the invention in amounts not above 30 wt. %, and in particular of 2wt. % to 20 wt. %.

In a further preferred embodiment, the agent according to the inventionis present portioned and ready-for-use in individual doses in a chamberformed of water-soluble material. A portion represents an independentdosing unit with at least one chamber, in which product to be dosed ispresent. A chamber is a space that is delimited by walls (by a film, forexample) and can also exist without the product to be dosed (ifnecessary, in a changed shaped). A surface coating or a layer of asurface coating thus does not constitute a wall according to the presentinvention.

The walls of the chamber are made of a water-soluble material. The watersolubility of the material can be determined by way of a square film ofsaid material (film: 22×22 mm having a thickness of 76 μm) fixed withthe aid of a square frame (edge length on the inside: 20 mm), accordingto the following measuring protocol. Said framed film is immersed in 800ml distilled water controlled to 20° C. in a 1-liter beaker glass havinga circular base area (Schott, Mainz, beaker glass 1000 mL, low shape),so that the surface area of the tensioned film is arranged at a rightangle with respect to the base area of the beaker glass, the upper edgeof the frame is located 1 cm beneath the water surface, and the loweredge of the frame is oriented parallel to the base area of the beakerglass in such a way that the lower edge of the frame extends along theradius of the base area of the beaker glass, and the center of the loweredge of the frame is arranged above the center of the radius of thebeaker glass bottom. The material dissolves, when stirred (stirringspeed of magnetic stirrer 300 rpm, stirring rod: 5 cm long), within 600seconds in such a way that individual solid particles can no longer bedetected with the naked eye.

The walls of the chambers, and thus the water-soluble wrappings of thewashing agents according to the invention are preferably formed by awater-soluble film material. Such water-soluble packagings can beproduced using either vertical form fill sealing methods or usingthermoforming methods.

The thermoforming method generally includes forming a first layer from awater-soluble film material so as to create bulges for receiving acomposition therein, filling the composition into the bulges, coveringthe bulges that are filled with the composition with a second layer madeof a water-soluble film material, and sealing the first and secondlayers together, at least around the bulges.

The water-soluble film material is preferably selected from polymers orpolymer mixtures. The wrapping can be formed of one layer, or of two ormore layers of the water-soluble film material. The water-soluble filmmaterials of the first layer and of the further layers, if such arepresent, can be the same or different.

It is preferable for the water-soluble wrapping to comprise polyvinylalcohol or a polyvinyl alcohol copolymer, and particularly preferably itconsists of polyvinyl alcohol or a polyvinyl alcohol copolymer.

Water-soluble films for producing the water-soluble wrapping arepreferably based on a polyvinyl alcohol, or a polyvinyl alcoholcopolymer, having a molecular weight in the range of 10,000 to 1,000,000gmol⁻¹, preferably of 20,000 to 500,000 gmol⁻¹, particularly preferablyof 30,000 to 100,000 gmol⁻¹, and in particular of 40,000 to 80,000gmol¹.

The polyvinyl alcohol is typically produced by the hydrolysis ofpolyvinyl acetate since the direct synthesis pathway is not possible.The same applies to polyvinyl alcohol copolymers produced accordinglyfrom polyvinyl acetate copolymers. It is preferred if at least one layerof the water-soluble wrapping comprises a polyvinyl alcohol having adegree of hydrolysis of 70 to 100 mol %, preferably 80 to 90 mol %,particularly preferably 81 to 89 mol %, and in particular 82 to 88 mol%.

Additionally, polymers selected from the group consisting of acrylicacid-containing polymers, polyacrylamides, oxazoline polymers,polystyrene sulfonates, polyurethanes, polyesters, polyethers,polylactic acid and/or mixtures of the above polymers can be added to afilm material that is suitable for producing the water-soluble wrapping.The co-polymerization of monomers underlying such polymers, eitherindividually or in mixtures of two or more, with vinyl acetate is alsopossible.

Preferred polyvinyl alcohol copolymers include an ethylenicallyunsaturated carboxylic acid, the salt thereof, or the ester thereof, inaddition to vinyl alcohol. In addition to vinyl alcohol, such polyvinylalcohol copolymers particularly preferably comprise acrylic acid,methacrylic acid, acrylic acid esters, methacrylic acid esters ormixtures thereof; among the esters, C₁₋₄ alkyl esters or hydroxyalkylesters are preferred. In addition to vinyl alcohol, likewise preferredpolyvinyl alcohol copolymers comprise ethylenically unsaturateddicarboxylic acids as further monomers. Suitable dicarboxylic acids are,for example, itaconic acid, maleic acid, fumaric acid and mixturesthereof, itaconic acid being particularly preferred.

Suitable water-soluble films for use in the wrappings of thewater-soluble packagings according to the invention are films sold byMonoSol LLC, for example, by the designation M8630, C8400 or M8900.Other suitable films include films by the designation Solublon® PT,Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical EuropeGmbH, or the VF-HP films from Kuraray.

The washing or cleaning agent portion, comprising the washing orcleaning agent and the water-soluble wrapping, can comprise one or morechambers. The water-soluble wrappings comprising one chamber can have asubstantially dimensionally stable spherical, spheroid-shaped, cubic,cuboid or pillow-shaped design having a circular, elliptic, square orrectangular basic shape. The agent can be present in one or morechambers, if present, of the water-soluble wrapping.

In a preferred embodiment, the water-soluble wrapping comprises twochambers. In this embodiment, the two chambers can each contain a solidpartial composition, or can each contain a liquid partial composition,or the first chamber contains a liquid partial composition and thesecond chamber contains a solid partial composition.

The proportions of the agents contained in the different chambers of awater-soluble wrapping comprising two or more chambers can have the samecomposition. Preferably, however, the agents in a water-soluble wrappingcomprising at least two chambers have partial compositions that differin at least one ingredient and/or in the content of at least oneingredient. A partial composition of such agents according to theinvention preferably comprises an enzyme and/or bleach activator, and afurther partial composition present separately therefrom comprises aperoxide bleaching agent, wherein the first partial composition, inparticular, does not comprise a peroxide bleaching agent, and the secondpartial composition, in particular, does not comprise an enzyme and doesnot comprise a bleach activator.

The portioned packaging in a water-soluble wrapping enables the user toplace one or, if desired, multiple, preferably one, of the portions intothe washing machine or dishwasher for use, and in particular in thedetergent dispenser of a washing machine, or in a receptacle forcarrying out a manual washing or cleaning process. Such portionedpackagings meet the consumer's desire for simplified dosing. After wateris added, the wrapping material dissolves, whereby the ingredients arereleased and able to develop the action thereof in the liquor. Awater-soluble wrapped portion preferably weighs 10 g to 35 g, inparticular 12 g to 28 g, and particularly preferably 12 g to 15 g,wherein the proportion of the water-soluble wrapping accounts for 0.3 gto 2.5 g, and in particular 0.7 g to 1.2 g, in the weight information.

The production of solid agents according to the invention does not poseany difficulties and be carried out in the known manner, for example byway of spray drying or granulation, wherein enzymes and potentialfurther thermally sensitive ingredients, such as bleaching agents, areoptionally added separately later. To produce agents having increasedbulk density, in particular in the range from 650 g/L to 950 g/L, amethod comprising an extrusion step is preferred.

Liquid or pasty agents according to the invention in the form ofsolutions comprising water customary solvents are generally produced bysimple mixing of the ingredients, which can be placed into an automaticmixer in substance or as a solution.

EXAMPLES Example 1: Production of 4-(3-hydroxypropyl)-guaiacol From Wood

As described in Angew. Chem. Int. Ed. 2014, 53, 8634 to 8639, sprucewood pellets and Raney nickel were suspended in a 2-propanol/watermixture and heated in the autoclave for 3 hours to 180° C. The resultantorganic oil was separated from the remaining solids, and from this4-(3-hydroxypropyl)-guaiacol was quantitatively isolated by way of balltube distillation.

Example 2: Production of Surfactants According to the Invention

A) Surfactant T1 of general formula (I), where R¹=n-octyl, R²=CH₃ andM=Na

30 mmol methyl iodide was slowly added to a solution of 15 mmol4-(3-hydroxypropyl)-guaiacol and 60 mmol potassium carbonate in 125 mldry acetone under argon. The reaction mixture was stirred for 24 hoursunder an argon atmosphere at 60° C. Thereafter, the reaction mixture wascooled, diluted with methyl-tert-butyl ether (MTBE) and quenched withwater. The reaction mixture was extracted with MTBE and washed withaqueous NaCl solution. The organic phase was dried over sodium sulfateand filtered, and the organic solvent was removed by way ofdistillation. The residue was distilled at reduced pressure, resultingin a yield of 86 percent of 4-(3-hydroxypropyl)-2-methoxyanisol. Theproduct was used further without additional purification.

1 mmol of the 4-(3-hydroxypropyl)-2-methoxyanisole thus obtained, in 12ml dimethyl sulfoxide, was mixed with 335 mg potassium-tert-butanolateand 3 mmol 1-n-octyl bromide and heated at 60° C. After the reaction wascomplete (ascertained by way of DC), the reaction mixture was extractedwith methyl-tert-butyl ether, the organic phase was separated, washedwith aqueous 2 wt. % NaHSO₃, water and aqueous NaCl solution, and afterthe organic phase was dried over Na₂SO₄, the solvent was removed by wayof distillation, and the raw product was purified by way of columnchromatography. This resulted in a yield of 93 percent of1,2-dimethoxy-4-(3-(oxtyloxy)propyl)benzene.

10 mmol of the 1,2-dimethyoxy-4-(3-(oxtyloxy)propyl)benzene thusobtained was reacted with 30 ml 98% H₂SO₄ at 5° C. and stirred for 30minutes at 5° C. The mixture was heated to room temperature whilestirring continued. After the reaction was complete (ascertained by wayof DC), the reaction mixture was poured into ice water and neutralizedwith NaOH. Water was removed by way of distillation, and the residue wasplaced in methanol. The resultant solution was filtered, and the solventwas removed by way of distillation. This resulted in a yield of 89% ofsurfactant T1 of general formula (I), where R¹=n-octyl, R²═CH₃ and M=Na.

B) Surfactant T2 of general formula (I), where R¹=n-tetradecyl, R²═H andM=Na

20 mmol 4-(3-hydroxypropyl)-guaiacol, 30 mmol benzyl bromide and 60 mmolpotassium carbonate were placed in 100 ml acetone and heated for 18hours under reflux. Thereafter, the reaction mixture was filtered andconcentrated by way of distillation at reduced pressure. The product wasisolated by way of ball tube distillation. This resulted in a yield of93 percent of 3-(4-(benzyloxy)-3-methoxyphenyl)propan-1-ol.

1 mmol of the 3-(4-(benzyloxy)-3-methoxyphenyl)propan-1-ol thusobtained, in 12 ml dimethyl sulfoxide, was mixed with 335 mgpotassium-tert-butanolate and 3 mmol 1-n-tetradecyl bromide and heatedat 60° C. After the reaction was complete (ascertained by way of DC),the reaction mixture was extracted with methyl-tert-butyl ether, theorganic phase was separated, washed with aqueous 2 wt. % NaHSO₃, waterand aqueous NaCl solution, and after the organic phase was dried overNa₂SO₄, the solvent was removed by way of distillation, and the rawproduct was purified by way of column chromatography. This resulted in ayield of 85 percent of1-(benzyloxy)-2-methoxy-4-(3-(tetradecyloxy)propyl)benzene.

A catalytic amount of Pd on carbon (Pd/C, 5%) was added to a solution of1 mmol of the 1-(benzyloxy)-2-methoxy-4-(3-(tetradecyloxy)propyl)benzenethus obtained in 20 MI dry tetrahydrofuran. After applying hydrogenpressure (5 bar), the reaction mixture was stirred for 8 hours at 40° C.Thereafter, the reaction mixture was cooled to room temperature, thecatalyst was removed by way of filtration over Celite, and the solventwas removed by way of distillation. The residue was distilled at reducedpressure, and the raw product was purified by way of columnchromatography. This resulted in a yield of 95 percent of2-methoxy-4-(3-(tetradecyloxy)propyl)phenol.

10 mmol of the 2-methoxy-4-(3-(tetradecyloxy)propyl)phenol thus obtainedwas reacted with 30 ml 98% H₂SO₄ at 5° C. and stirred for 30 minutes at5° C. The mixture was heated to room temperature while stirringcontinued. After the reaction was complete (ascertained by way of DC),the reaction mixture was poured into ice water and neutralized withNaOH. Water was removed by way of distillation, and the residue wasplaced in methanol. The resultant solution was filtered, and the solventwas removed by way of distillation. This resulted in a yield of 83% ofsurfactant T2 of general formula (I), where R¹=n-tetradecyl, R²═H andM=Na.

C) Surfactant T3 of general formula (I), where R¹=n-decyl, R²═H and M=Na

Using n-decyl bromide instead of 1-n-tetradecyl bromide, the surfactantaccording to general formula (I), where R¹=n-decyl, R²═H and M=Na (T3)was obtained analogously to the procedure described in B) (yields in theindividual steps in %: 93/87/92/81).

Example 3: Measurement of the Critical Micelle Concentration (CMC)

The CMC of the surfactants produced in Example 2 was determined bymeasuring the surface tension of an aqueous solution of the substancesas a function of the concentration at 25° C. and a pH of 8.5.

TABLE 1 CMC values Substance CMC (g/L) T1 1.0 T2 0.01 T3 0.2

Example 4: Measurement of the Interfacial Tension

The interfacial tension of a respective aqueous solution of thesubstances described in Example 3 and, for comparison, that ofpetrochemically produced Na dodecyl benzene sulfonate (V1)(concentration 1 g/L in each case) over triolein at pH 8.5 and 25° C.was measured by way of the spinning drop method. After 20 minutes, thevalues listed in Table 2 were obtained.

TABLE 2 Interfacial tension values Substance γ (mN/ml) V1 0.5 V2 0.5 T20.9 T3 0.3

It is apparent that interfacial tensions of the surfactants according tothe invention did not deviate significantly from those of the frequentlyused, petrochemically based surfactant.

What is claimed is:
 1. An anionic surfactant of general formula (I),

in which R¹ denotes a linear or branched alkyl functional group having 6to 20 carbon atoms, R² denotes H or CH3, and M denotes hydrogen, analkali metal or an N⁺R³R⁴R⁵ grouping, in which R³, R⁴ and R⁵,independently of one another, denote hydrogen, an alkyl group having 1to 6 carbon atoms or a hydroxyalkyl group having 2 to 6 carbon atoms. 2.A method for producing an anionic surfactant of general formula (I),

in which R¹ denotes a linear or branched alkyl functional group having 6to 20 carbon atoms, R² denotes H or CH3, and M denotes hydrogen, analkali metal or an N⁺R⁴R⁵ grouping, in which R³, R⁴ and R⁵,independently of one another, denote hydrogen, an alkyl group having 1to 6 carbon atoms or a hydroxyalkyl group having 2 to 6 carbon atoms,comprising the step of O-alkylation of the hydroxypropyl group or4-(3-hydroxypropyl)-guaiacol or 4-(3-hydroxypropyl)-2-methoxyanisole andsubsequent sulfonation, where M denotes an alkali metal or an N⁺R³R⁴R⁵grouping, in which R³, R⁴ and R⁵, independently of one another, denotehydrogen, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkylgroup having 2 to 6 carbon atoms.
 3. A washing or cleaning agent,comprising an anionic surfactant of general formula (I),

in which R¹ denotes a linear or branched alkyl residue having 6 to 20carbon atoms, R² denotes H or CH3, and M denotes hydrogen, an alkalimetal or an N⁺R³R⁴R⁵ grouping, in which R³, R⁴ and R⁵, independently ofone another, denote hydrogen, an alkyl group having 1 to 6 carbon atomsor a hydroxyalkyl group having 2 to 6 carbon atoms.
 4. The washing orcleaning agent according to claim 3, comprising 1 wt. % to 99 wt. % ofthe surfactant of general formula (I).
 5. The washing or cleaning agentaccording to claim 4, additionally comprising up to 99 wt. % of afurther surfactant.
 6. The washing or cleaning agent according to claim4, wherein the washing or cleaning agent is particulate and comprisesbuilders.
 7. The washing or cleaning agent according to claim 4, whereinthe washing or cleaning agent is liquid and comprises 1 wt. % to 90 wt.% water, water-miscible solvent or a mixture of water and water-misciblesolvent.
 8. The washing or cleaning agent according to claim 4, whereinthe washing or cleaning agent is present portioned and ready-for-use inindividual doses in a chamber formed of water-soluble material.
 9. Theanionic surfactant, according to claim 1, of general formula (I),

in which R¹ denotes a linear or branched alkyl functional group having 8to 14 carbon atoms, R² denotes H or CH3, and M denotes hydrogen, analkali metal or an N⁺R³R⁴R⁵ grouping, in which R³, R⁴ and R⁵,independently of one another, denote hydrogen, an alkyl group having 1to 6 carbon atoms or a hydroxyalkyl group having 2 to 6 carbon atoms.10. The method, according to claim 2, for producing an anionicsurfactant of general formula (I),

in which R¹ denotes a linear or branched alkyl functional group having 8to 14 carbon atoms, R² denotes H or CH3, and M denotes hydrogen, analkali metal or an N⁺R³R⁴R⁵ grouping, in which R³, R⁴ and R⁵,independently of one another, denote hydrogen, an alkyl group having 1to 6 carbon atoms or a hydroxyalkyl group having 2 to 6 carbon atoms,comprising the step of O-alkylation of the hydroxypropyl group or4-(3-hydroxypropyl)-guaiacol or 4-(3-hydroxypropyl)-2-methoxyanisole andsubsequent sulfonation, where M denotes an alkali metal or an N⁺R³R⁴R⁵grouping, in which R³, R⁴ and R⁵, independently of one another, denotehydrogen, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkylgroup having 2 to 6 carbon atoms.
 11. The method, according to claim 2,for producing an anionic surfactant of general formula (I),

in which R¹ denotes a linear or branched alkyl functional group having 6to 20 carbon atoms, R² denotes H or CH3, and M denotes hydrogen, analkali metal or an N⁺R³R⁴R⁵ grouping, in which R³, R⁴ and R⁵,independently of one another, denote hydrogen, an alkyl group having 1to 6 carbon atoms or a hydroxyalkyl group having 2 to 6 carbon atoms,comprising the step of O-alkylation of the hydroxypropyl group or4-(3-hydroxypropyl)-guaiacol or 4-(3-hydroxypropyl)-2-methoxyanisole andneutralization by way of subsequent reaction with MOH, where M denotesan alkali metal or an N⁺R³R⁴R⁵ grouping, in which R³, R⁴ and R⁵,independently of one another, denote hydrogen, an alkyl group having 1to 6 carbon atoms or a hydroxyalkyl group having 2 to 6 carbon atoms.12. The washing or cleaning agent, according to claim 3, comprising ananionic surfactant of general formula (I),

in which R′ denotes a linear or branched alkyl residue having 8 to 14carbon atoms, R² denotes H or CH3, and M denotes hydrogen, an alkalimetal or an N⁺R³R⁴R⁵ grouping, in which R³, R⁴ and R⁵, independently ofone another, denote hydrogen, an alkyl group having 1 to 6 carbon atomsor a hydroxyalkyl group having 2 to 6 carbon atoms.
 13. The washing orcleaning agent according to claim 4, characterized by comprising 3 wt. %to 85 wt. % of the surfactant of general formula (I).
 14. The washing orcleaning agent according to claim 5, characterized by additionallycomprising 3 wt. % to 85 wt. % of a further surfactant.
 15. The washingor cleaning agent according to claim 6, characterized by beingparticulate and comprising builders in an amount in the range of 1 wt. %to 60 wt. %.
 16. The washing or cleaning agent according to claim 7,characterized by being liquid and comprising 10 wt. % to 85 wt. % water,water-miscible solvent or a mixture of water and water-miscible solvent.